2, 5-diamino-1-thiadiazine-3, 4 and derivatives thereof



Patented Jan. 2, 1951 if 1' TI" 2,5 DIAMINo-'1 'rniAn1AzrN -s,4 ANDDERIVATIVES THEREOF Henry A. Walter, Longmcadow, Mass., ass'ignortoMonsanto Chemical Company, St. Louis,

Mo., a corporation of Delaware No Drawing.

This invention relates to diazines and resins made therefrom. Moreparticularly, the invention relates to 2,5-diaminol-thiadiazine-3,4derivatives thereof and resins prepared therefrom.

An object of this invention is to provide 2,5-diamino-1-thiadiazine-3,4.

A further object is to provide derivatives of2,5-diamino-1-thiadiazine-3,4.

Another object is to provide thermosetting resins based on2,5-diamino-1-thiadiazine-3,4 and its derivatives.

These and other objects are attained by reacting thiosemicarbazide withchloracetamide or an alkyl substituted chloracetamideand then reactingthe product with an aldehyde.

The following examples are given in illustration and are not intended aslimitations of the scope of this invention. Where parts are mentioned,they are parts by weight.

Example I A mixture of 100 parts of thiosemicarbazide and 86 parts ofchloracetamide was dissolved in a 50-50 solution of ethanol in water.Re-

action was rapid at a. temperature of about 70 of fine needles wasobtained. The crystals had a melting point of over 250 C. The crystalswere identified as 2,5-diamino-l-thiadiazine-S,4.

Example II A solution of 100 parts of thiosemicarbazide in aqueousethanol was mixed with a solution of 100 parts of a-chloropropionamidein aqueous ethanol. 011 mix ng the two solutions, rapid reaction wasobserved and a precipitate developed. The precipitate was recovered byfiltration and dissolved in hot aqueous sodium bicarbonate. On cooling,fine needle-like crystals developed which were identified as2,5-diamino-6- methyl-1-thiadiaz ne-3,4.

The compounds of this invention have the following structural formula fA lit-n4 6(l3-R Na 1s HNH wherein R may be hydrogen, alkyl or aryl.

They are prepared by reacting thiosemicarbazide with a compound havingthe formula R-CHCl-CONHz wherein B may be hydrogen, alkyl or aryl. Thus,when R is hydrogen, the

and an alcohol.

Application November 24, 1948, Serial No. 61,915

compound is chloracetamide, when R is methyl the compound isa-chloropropionamide, when R is phenyl the compound is a-phenyl,e-chloracetamide. The compounds may be named from the acid from whichthey are derived or as substitution products of acetamide. Thus,a-ChlOlO- propionamide may also be called a-rnethyle-chloracetamide anda-phenyl a chloracetamide may be called a-chl-orobenzamide. It ispreferred touse approximately equimolar quantities of the two reactantssince a large excess of either component tends to produce undesirableby-products in substantial amounts.

The reaction between thiosemicarbazide and the chloracetamides may beeasily carried out at temperatures ranging from 50-100 C. althoughhigher temperatures may be used if desired. The reaction is convenientlycarried out in ethanol-water solutions, especially since the productsare insoluble therein and may be easily recovered by a simple filtrationprocess. The precipitate must then be treated with hot sodiumbicarbonate to obtain the free base. Other compounds than sod umbicarbonate may be used includin sodium hydroxide, sodium carbonate,potassium carbonate, etc.

The compounds of this invention are particularly useful for thepreparation of thermosetting molding powders and coating resins. Theresins are prepared by reacting the thiadiaz nes with aldehydes,especially formaldehyde under alkaline conditions with or withoutfurther modification with an alcohol.

Example III A mixture of 1 mol of 2,5-diamino-1-thiadiazine-3,4 with 2mols of formaldehyde was heated at reflux temperature and atmosphericpressure at a pH of about 89 for about 1 hour. The product was anaqueous suspension of a light brown, fus ble resin. The resin could berecovered by dehydration and molded with or without conventionaladditives such as fillers, pigments, dyes, lubricants, etc. The resincould be cured to the infu ible state by heating at from IOU-200 C. Thetime necessary to effect a complete cure could be shortened by the useof acidic curing catalysts.

If it is des red to prepare a coating resin. the thiadiazines may bereacted with an aldehyde Any alcohol may be used such as methanol,ethanol, butanol, stearyl alcohol, cetyl a coho ben'zvl alcohol,cvclohexanol, etc. All three ingredients may be reacted together at onetime under alkaline conditions, or the thiadiazine and aldehyde may bereacted together und r a kali e condit ons. and the roduct reacted withthe alcohol under acid conditions.

The alcohol-modified resins are compatible with other coating resinssuch as alkyd resins and the coatings made therefrom have a high gloss,excellent alkali-resistance and excellent resistance to aging.

The resinous condensation products of this invention are furtherdescribed and claimed in my continuation-impart application Serial No.

120,420, filed October 8, 1949.

It is obvious that many variations may be made in the products andvprocesses of this invention without departing from the spirit and scopethereof as defined by the appended claims.

What is claimed isz; 1. A compound corresponding to the formula n-If-HQ/ EK v H-N4 6C-R 7' 4 wherein'R is a radical taken from the groupconsisting of hydrogen, methyl and phenyl radicals. V

'2. 2,5-diamino-1-thiadazine-3,4.

3. 2,5-dia1nino-6-methy1 1-thiadiazine-3,4.

- HENRY A. WALTER.

V V I REFERENCES CITED 7 The following'references are of record in thefile of this patent:

UNITED STATES PATENTS Number Name Date 2,449,520 Walter 2 Sept. 14, 1948REFERENCES 1 nose; chem. Abstn, vol. 20 (1926). Bosez' Chem. Abstrgjvol.21 (1927).

Walter Nov. 16, 1948

1. A COMPOUND CORRESPONDING TO THE FORMULA